This invention relates to new 17.alpha.-halovinylestranes and their pharmaceutical use.
17.alpha.-(E-2-iodovinyl)-1,3,5(10)-estratriene-3,17.beta.-diol in the E-configured estrogen series is known from the works of Hanson et al. (J. Nucl. Med. 23 (1982) 431). Also, the corresponding 3-methyl ether (Kabalka et al., Syn. Commun. 11 (1981) 247), the corresponding radioiodine compound (Kabalka et al., J. Label Comp. Radiopharm. 19 (1982) 795) and the 11.beta.-methoxy compound, i.e., 17.alpha.-(E-2-iodovinyl-11.beta.-methoxy-1,3,5(10)-estratriene-3,17.beta. -diol (Jagoda et al., J. Nucl. Med. 25 (1984) 472) have already been produced. 17.alpha.-(Z-2-bromovinyl)-methoxy-1,3,5(10)-estratrien-17.beta.-ol is known in the Z-configured estrogen series (Kabalka et al., Syn. Commun. 13 (1983) 1027).
Synthesis of these halogen vinyl steroids and also of radioiodovinyl compounds proceeds by 17.alpha.-(E-2-tributylstannylvinyl) derivatives or by the 17.alpha.-(E-2-vinylborane) compound. These are reacted with iodine or [.sup.125 I]iodine. The 17.alpha.-tributylstannyls are produced from ethinylestradiol or its 3-methyl ether, e.g., by reaction with tributyltin hydride with addition of a radical former, e.g., .alpha.-.alpha.'-azoisobutyronitrile in tetrahydrofuran, while E-17.alpha.-vinylborane is formed by hydroboration with organoboranes, e.g., catecholborane.